The subject of the present invention is a topical composition, in particular a cosmetic composition, which can be provided in the form of a stick or of a supple paste and which is capable of being used for caring for and/or making up the skin, semimucous membranes (such as the lips) and/or mucous membranes (such as the interior of the lower eyelids) of human beings and more especially the lips of the face.
Cosmetic or pharmaceutical compositions, such as lipsticks and foundations, generally comprise fatty substances, such as oils, pasty compounds and waxes, as well as a particulate phase generally composed of fillers and of pigments. They can also contain cosmetic or dermatological active principles (vitamins, screening agents, moisturizers). These compositions, when they are applied on the skin, the mucous membranes or the semimucous membranes, exhibit the disadvantage of transferring. This is understood to mean that the composition is capable of being deposited, at least in part, on certain substrates with which it is brought into contact, such as, for example, a glass, a cup, an item of clothing or the skin. On being deposited, the composition leaves a mark on the substrate. The result is thus a mediocre persistence of the composition on the skin or the mucous membranes, requiring it to be reapplied regularly. Moreover, the appearance of unacceptable marks on certain items of clothing and in particular on the collars of shirts or blouses might dissuade some consumers from using this type of makeup.
Another disadvantage of these compositions lies in the problem of migration. It has been found that certain cosmetic compositions have a tendency to spread into the fine lines and/or wrinkles of the skin, in the case of foundations; into the fine lines which surround the lips, in the case of lipsticks; and into the folds of the eyelid, in the case of eyeshadows. The appearance has also been found, in the case in particular of eyeshadows, of streaks in the makeup, due to the movements of the eyelids.
All these phenomena produce an unsightly effect which it is very clearly desirable to avoid.
For several years, many cosmetic scientists have been interested in xe2x80x9ctransfer-freexe2x80x9d cosmetic compositions, in particular xe2x80x9ctransfer-freexe2x80x9d lipstick or foundation compositions. Thus, Patent Application JP-A-61-65809 envisaged xe2x80x9ctransfer-freexe2x80x9d lipstick compositions containing from 1 to 70% by weight of pulverulent silicone resin with silicate repeating units (or with a three-dimensional network) containing pendant alkylated or phenylated chains, the alkylated chains containing 1 to 6 carbon atoms, from 10 to 98% by weight of a cyclic volatile silicone oil and pulverulent fillers. However, these compositions exhibit the disadvantage of being liquid and thus rather inconvenient to use or at the very least far from the conventional concept of a lipstick in the form of a stick, thus limiting the number of consumers liable to use this type of lipstick. Moreover, the film obtained on the lips after evaporation of the silicone oil exhibits the disadvantage of becoming uncomfortable with time (feeling of desiccation and of tightness).
More recently, xe2x80x9ctransfer-freexe2x80x9d lipsticks containing a cyclic or linear volatile silicone and a silicone resin containing a pendant esterified chain having at least 12 carbon atoms have been envisaged in Patent Application EP-A-602,905. The lipstick film exhibits in particular the disadvantage of lacking comfort on application, in particular of being too dry.
More recently still, the use has been envisaged, in these transfer-free compositions, of silicone resins modified by fluorinated groups (see the document EP-A 661,042). These resins, which are again provided in the pulverulent form, also result in compositions which are not very comfortable, desiccating and tightening the lips or the skin on which they are applied. Moreover, these resins are difficult to employ. Thus, it is preferable to mix them, prior to their use, with a volatile silicone oil, which involves an additional premixing stage, resulting in a significant additional cost during industrial production. Moreover, the necessary presence of a silicone oil in the introduction of the said resin results in an additional formulating constraint.
Generally, it is now known that, while the combination of volatile oils with certain compounds, in particular silicone compounds, makes it possible to obtain a satisfactory xe2x80x9ctransfer-freexe2x80x9d result, it nevertheless exhibits the disadvantage of resulting, after evaporation of the volatile substances, in a film of non-optimum comfort, in particular because it is impossible to add oils other than silicone oils to these compositions while retaining a correct xe2x80x9ctransfer-freexe2x80x9d quality. This is because hydrocarbon oils, which are known to contribute in particular comfort to a cosmetic or dermatological composition, have the disadvantage of increasing the transfer of such a composition.
Now, following in-depth studies, the inventors have demonstrated that, unexpectedly and surprisingly, it was possible to prepare a so-called xe2x80x9ctransfer-freexe2x80x9d cosmetic composition which makes it possible, in particular, to obtain a film which does not transfer and which does not migrate and which exhibits improved cosmetic properties with respect to those of the xe2x80x9ctransfer-freexe2x80x9d products of the prior art, in particular slip, non-tightness, softness and comfort properties.
This composition, with improved comfort with respect to the prior art, makes it possible to limit the transfer and/or the migration of the composition and thus makes it possible to improve the mechanical strength thereof, in particular toward rubbing and/or toward pressure.
A subject of the present invention is thus a topical composition comprising a fatty phase which contains at least one volatile compound, at least one wax and at least one nonvolatile liquid fatty substance,
wherein the fatty phase contains at least one fluorosilicone compound of formula (I): 
in which:
R represents, or independently represents, in the case when n is greater than 1, a linear or branched divalent alkylene group having from 1 to 6 carbon atoms, preferably a divalent methylene, ethylene, propylene or butylene group,
Rf represents, or independently represents, in the case when n is greater than 1, a fluoroalkyl radical, in particular a perfluoroalkyl radical, having from 1 to 9 carbon atoms, preferably from 1 to 4 carbon atoms,
R1 represents, independently of one another, a C1-20 alkyl radical, a hydroxyl radical or a phenyl radical,
m ranges from 0 to 150, preferably from 20 to 100, and
n ranges from 1 to 300, preferably from 1 to 100, and
the non-fluoro, nonvolatile liquid fatty substance(s) and/or non-fluoro wax(es) are selected so as to satisfy the following relationship:
xe2x80x830xe2x89xa6xcex94xcex4xe2x89xa65
in which:
xcex94xcex4[4xc3x97(xcex4D non-fluoro waxxe2x88x92xcex4D non-fluoro, nonvolatile liquid fatty substance)2+(xcex4P non-fluoro waxxe2x88x92xcex4P non-fluoro, nonvolatile liquid fatty substance)2+(xcex4H non-fluoro waxxe2x88x92xcex4H non-fluoro, nonvolatile liquid fatty substance)2]xc2xd.
In this formula, xcex4D characterizes the London dispersion forces resulting from the formation of dipoles induced during molecular impacts; xcex4P characterizes the Debye interaction forces between permanent dipoles; and xcex4H characterizes the specific interaction forces (hydrogen bond, acid/base, donor/acceptor type and the like.
Another subject of the invention is the use, in a transfer-free topical composition, of a fatty phase as mentioned above, in order to obtain a composition exhibiting good slip, non-tightness, softness and/or comfort properties.
xe2x80x9cTransfer-freexe2x80x9d composition is understood to mean in particular, in the present description, a composition which does not transfer or transfers only to a very slight extent, that is to say which is not deposited on and/or does not stain and/or does not adhere to a substrate with which it is brought directly into contact. A composition of foundation or tinted cream type which does not stain a shirt or blouse (thus in particular resistant to rubbing due to the movement of the face and of the neck) as well as a composition of lipstick type which does not stain a substrate, such as a glass, a cup or the skin (thus resistant to the pressure due to the application of the lips on the said substrate) are in particular considered as xe2x80x9cnon-transferxe2x80x9d according to the present invention.
A further subject of the invention is a process for limiting, decreasing and/or preventing the transfer of a composition for making up or for caring for the skin, mucous membranes, semimucous membranes or superficial body growths which consists in introducing, into the composition, a fatty phase as defined above.
The composition of the present invention exhibits a mechanical strength, in particular toward rubbing and/or toward pressure, thus a resistance to rubbing, which is appropriate and is considered as very comfortable, on application and throughout the day.
The composition according to the invention especially finds a particularly advantageous application in the field of caring for and/or of making up the skin, mucous membranes, semimucous membranes and superficial body growths. Mucous membrane is understood to mean in particular the inner part of the lower eyelid, semimucous membranes includes, more particularly, the meaning of the lips of the face and superficial body growths is understood to mean the eyelashes, eyebrows, hair and nails.
Thus, the invention finds a very particular application in the field of products for making up the lips of the face but also products for caring for the lips, as well as in the field of products for making up and caring for the skin, such as foundations, concealers, self-tanning agents or antisun products.
A further subject of the invention is consequently a transfer-free composition for making up or for caring for the lips containing a fatty phase as defined above.
The composition according to the invention thus comprises at least one fluorosilicone compound, which can be a volatile compound, a nonvolatile liquid fatty substance, a wax or a mixture of these compounds. In a preferred embodiment, the fluorosilicone compound is provided in the form of a nonvolatile liquid fatty substance.
The specific combination of the fluorosilicone compound with specific oils and/or waxes, the entire mixture being combined with a volatile compound, makes it possible to obtain notable xe2x80x9ctransfer-freexe2x80x9d properties while resulting in a film which is very highly comfortable on the substrate on which it is applied.
During the preparation of a composition according to the invention, a homogeneous mixture is obtained in which the fluorosilicone compound is completely dissolved or dispersed. When the composition is applied on a substrate, for example on the lips, the volatile compounds rapidly evaporate. Without being bound by the present explanation, it is possible to envisage that, in the composition remaining on the lips, the fluorosilicone compound will have a tendency to migrate toward the most distant part of said substrate, in other words will have a tendency to xe2x80x9cclimbxe2x80x9d to the surface of the deposited film, which will have the consequence of leaving, in the part which is closest to the substrate and thus in direct contact with said substrate, principally the other fatty compounds and in particular the hydrocarbon oils which contribute comfort.
The fluorosilicone compound can preferably be represented by the following formula (II): 
in which:
R represents, or independently represents, in the case when n is greater than 1, a linear or branched divalent alkylene group having from 1 to 6 carbon atoms, preferably a divalent methylene, ethylene, propylene or butylene group,
Rf represents, or independently represents, in the case when n is greater than 1, a fluoroalkyl radical, in particular a perfluoroalkyl radical, having from 1 to 9 carbon atoms, preferably from 1 to 4 carbon atoms,
m ranges from 0 to 150, preferably from 20 to 100, and
n ranges from 1 to 300, preferably from 1 to 100.
In an even more preferred embodiment, the fluorosilicone compound used according to the invention has the following formula (III): 
with
R representing, or independently representing, in the case when n is greater than 1, a divalent methylene, ethylene, propylene or butylene group,
m ranging from 0 to 80, and
n ranging from 1 to 30.
Such compounds are in particular those sold by Shin Etsu under the names xe2x80x9cX22-819xe2x80x9d, xe2x80x9cX22-820xe2x80x9d, xe2x80x9cX22-821xe2x80x9d and xe2x80x9cX22-822xe2x80x9d or alternatively xe2x80x9cFL-100xe2x80x9d.
It is very clearly possible to use a mixture of several fluorosilicone compounds. The nonvolatile liquid fatty substances can in particular replace all or part of the liquid fatty substances of the composition.
Moreover, the composition according to the invention can comprise any compound known to a person skilled in the art for the type of application envisaged which does not destroy the desired properties.
In a preferred embodiment, the composition is anhydrous.
The fluorosilicone compound can preferably be present in the composition in the proportion of 0.1 to 40% by weight, preferably 3 to 30% by weight, with respect to the total weight of the composition.
The composition according to the invention preferably comprises at least one compound which is volatile at room temperature (20-25xc2x0 C.), which can thus be fluorinated or non-fluorinated. Volatile compound is understood to mean, in the present description, any compound capable of evaporating on contact with the skin. Use is preferably made of volatile oils with a flashpoint sufficiently high to enable these oils to be used in formulation and sufficiently low for the desired evanescent effect to be obtained. Volatile oils are preferably employed with a flashpoint of the order of 40-100xc2x0 C.
These volatile compounds can in particular be selected, alone or as a mixture, from hydrocarbon oils and/or silicone oils, which are cyclic or linear.
Mention may be made, alone or as a mixture, among volatile silicone oils, of
volatile cyclic silicones having from 3 to 8 silicon atoms and preferably from 4 to 6. Examples are cyclotetradimethylsiloxane, cyclopentadimethylsiloxane and cyclohexadimethylsiloxane,
cyclocopolymers of the dimethylsiloxane/methylalkylsiloxane type, such as Silicone FZ 3109, sold by the company called Union Carbide, which is a dimethylsiloxane/methyloctylsiloxane cyclocopolymer,
volatile linear silicones having from 2 to 9 silicon atoms. Examples are hexamethyldisiloxane and a PDMS of low viscosity (1 cSt). Mention may alternatively be made of alkyltrisiloxanes, such as hexylhepta-methyltrisiloxane or octylheptamethyltrisiloxane.
Mention may be made, among volatile hydrocarbon oils, of C8-C15 isoparaffins and in particular isododecane.
The composition according to the invention can preferably comprise 8 to 99% by weight, more preferably 15 to 85% by weight and most preferably 30 to 70% by weight of volatile compounds with respect to the total weight of the composition.
The composition also comprises at least one wax which can be fluorinated or non-fluorinated or a mixture of different waxes, so as to help in conferring, in particular, mechanical strength on the composition, when it is provided in the form of a stick. When it is provided in the form of a supple paste or a cast product, the composition according to the invention can comprise a lower amount of wax.
Any wax known in the prior art can be employed, among which, alone or as a mixture, may be mentioned waxes of animal, vegetable, mineral and synthetic origin, such as microcrystalline waxes, paraffin, petrolatum, petroleum jelly, ozokerite, montan wax, beeswax, lanolin and its derivatives, candelilla, ouricury, carnauba and Japan waxes, cocoa butter, sugarcane or cork fiber waxes, hydrogenated oils which are solid at 25xc2x0 C., ozokerites, fatty esters and glycerides which are solid at 25xc2x0 C., polyethylene waxes and waxes obtained by the Fischer-Tropsch synthesis, silicone waxes and in particular alkylsilicone waxes, as well as fluorinated waxes, and their mixtures.
The waxes taking part in the composition can preferably exhibit a melting point greater than approximately 45xc2x0 C. and in particular greater than 55xc2x0 C., and/or a needle penetration index at 25xc2x0 C. preferably of from 3 to 40.
The composition preferably comprises 0.5 to 30% by weight of wax, in particular 5 to 20% by weight, with respect to the total weight of the composition.
Moreover, the composition comprises at least one nonvolatile liquid fatty substance, which can be fluorinated or non-fluorinated. Liquid fatty substance is understood to mean a compound having a melting point of less than approximately 30-35xc2x0 C., in contrast to solid fatty substances, such as waxes, which have a melting point greater than approximately 50xc2x0 C.
Mention may be made, among liquid fatty substances which can be envisaged, of any nonvolatile liquid fatty substance known to a person skilled in the art for the application envisaged. Mention may particularly be made of oils of vegetable, mineral, animal, synthetic and/or silicone origin, and their mixtures.
Mention may be made, among silicone oils, of phenylated silicone oils, in particular of polyphenylmethylsiloxane or phenyltrimethicone type, and in particular of the oils corresponding to the following formula: 
in which
R is independently a saturated or unsaturated, linear or branched C1-30 alkyl radical, an aryl radical or an aralkyl radical, in C7 and C60,
n is an integer ranging from 0 to 100,
m is an integer ranging from 0 to 100, with the proviso that the sum m+n is selected from 1 to 100.
Mention may alternatively be made of poly(C1-C20)alkylsiloxanes in which the alkyl group is saturated or unsaturated and linear or branched, and in particular those with terminal trimethylsilyl groups, among which mention may be made of linear polydimethylsiloxanes and of alkylmethylpolysiloxanes, alkyldimethicones or silicones modified by aliphatic and/or aromatic groups or by functional groups, such as hydroxyl, thiol and/or amine groups.
Mention may be made, among hydrocarbon oils of animal, vegetable, mineral or synthetic origin, of the oils formed by esters of fatty acids and of polyols, in particular liquid triglycerides, for example sunflower oil, maize oil, soybean oil, cucumber oil, liquid paraffin, liquid petrolatum, perhydrosqualene, groundnut oil, sweet almond oil, macadamia oil, grape seed oil, rapeseed oil, coconut oil, calophyllum oil, palm oil, castor oil, avocado oil, apricot oil, sesame oil, jojoba oil, olive oil or cereal germ oils, fish oils, glyceryl tricaprate/caprylate, fatty acid esters, alcohols, acetylglycerides, octanoates, decanoates or ricinoleates of alcohols or of polyalcohols, fatty acid triglycerides, glycerides, oils of formula R1COOR2, in which R1 represents the residue of a higher fatty acid containing from 7 to 19 carbon atoms and R2 represents a branched hydrocarbon chain containing from 3 to 20 carbon atoms, for example purcellin oil or wheat germ oil, and their mixtures.
In a preferred embodiment, the oils present in the composition are mainly hydrocarbons.
The composition according to the invention can preferably comprise 1 to 50% by weight of nonvolatile liquid fatty substance, in particular from 1 to 40% and better still from 5 to 30%, by weight.
Mention may be made, among other fatty substances capable of being present in the composition, of silicone gums and pasty fatty substances of vegetable, mineral, animal, synthetic and/or silicone origin. These fatty substances can in particular be chosen in a way varied by persons skilled in the art in order to prepare a composition having the desired properties, for example of consistency or of texture. These fatty substances can be both hydrocarbons and silicones, which makes it possible to adapt the properties of the film, in particular as regards the comfort on the lips or the skin of human beings.
The non-fluorinated, nonvolatile, liquid fatty substance(s) and/or the non-fluorinated wax(es) are selected so as to verify the following relationship:
xe2x89xa6xcex94xcex4xe2x89xa65
and preferably
xcex94xcex4xe2x89xa64
The distance xcex94xcex4 represents the distance in Hansen space between the point representing the wax or the mixture of waxes and the point representing the nonvolatile liquid fatty substance or the mixture of nonvolatile liquid fatty substances.
The volatile compounds, the fluorinated nonvolatile liquid fatty substances and the fluorinated waxes are not taken into consideration during the calculation of the distance xcex94xcex4.
The distance xcex94xcex4 can be calculated in the following way:
xcex94xcex4=[4xc3x97(xcex4D waxxe2x88x92xcex4D nonvolatile liquid fatty substance)2+(xcex4P waxxe2x88x92xcex4P nonvolatile liquid fatty substance)2+(xcex4H waxxe2x88x92xcex4H nonvolatile liquid fatty substance)2]xc2xd.
The definition of fatty substances in the three-dimensional solubility space according to Hansen is described in the article by C. M. Hansen: xe2x80x9cThe Three-dimensional Solubility Parametersxe2x80x9d, J. Paint Technol., 39, 105 (1967), the disclosure of which is specifically incorporated by reference herein.
According to the space described by Hansen:
xcex4D characterizes the London dispersion forces resulting from the formation of dipoles induced during molecular impacts;
xcex4P characterizes the Debye interaction forces between permanent dipoles;
xcex4H characterizes the specific interaction forces (hydrogen bond, acid/base, donor/acceptor type and the like);
The parameters xcex4P, xcex4H and xcex4D are generally expressed in (J/cm3)xc2xd.
In the composition according to the invention, any fatty substance or mixture of fatty substances satisfying the above relationships can be used. In this case, the solubility parameters of the mixture are determined from those of the fatty substances taken separately, according to the following relationships:             δ      Dmix        =                  ∑        i            ⁢              xi        ⁢                  xe2x80x83                ⁢                  δ          Di                      ;      xe2x80x83    ⁢            δ      Pmix        =                            ∑          i                ⁢                  xi          ⁢                      xe2x80x83                    ⁢                      δ            Pi                    ⁢                      xe2x80x83                    ⁢          and          ⁢                      xe2x80x83                    ⁢                      δ            Hmix                              =                        ∑          i                ⁢                  xi          ⁢                      xe2x80x83                    ⁢                      δ            Hi                              
where xi represents the fraction, by volume, of the fatty substance i in the mixture. It is within the capability of a person skilled in the art to determine the amounts of each fatty substance in order to obtain a mixture of fatty substances which satisfies the above relationships.
The composition can also comprise a particulate phase, which can comprise pigments and/or pearlescent agents and/or fillers commonly used in cosmetic and dermatological compositions. Pigments should be understood as comprising white or colored, inorganic or organic particles intended to color and/or opacify the composition. Fillers should be understood as comprising colorless or white, inorganic or synthetic, lamellar or non-lamellar particles intended to give body or stiffness to the composition, and/or softness, matteness and uniformity to the makeup. Pearlescent agents should be understood as comprising iridescent particles which reflect light.
The pigments can be present in the composition in the proportion of 0 to 15% by weight of the final composition and preferably in the proportion of 3 to 12% by weight. They can be white or colored, inorganic and/or organic, and of conventional or nanometric size. Mention should be made of titanium, zirconium or cerium dioxides, as well as of zinc, iron or chromium oxides, ferric blue, carbon black, ultramarines (aluminosilicate polysulfides), manganese pyrophosphate and certain metal powders, such as those of silver or of aluminum. Mention may alternatively be made of the lakes commonly employed to confer a makeup effect on the lips and on the skin, which are calcium, barium, aluminum or zirconium salts, acid dyes, such as hydrohalide dyes, azo dyes, anthraquinone dyes, and the like.
The pearlescent agents can be present in the composition in the proportion of 0 to 20% by weight, preferably at a level of the order of 1 to 10% by weight.
Mention may be made, among the pearlescent agents which can be envisaged, of natural mother-of-pearl, mica covered with titanium oxide, with iron oxide, with natural pigment or with bismuth oxychloride, and colored titanium oxide-coated mica.
The fillers, which can be present in a proportion of 0 to 30% by weight, preferably 1 to 15%, in the composition, can be inorganic or synthetic, lamellar or non-lamellar. Mention may be made of talc, mica, silica, kaolin, nylon or polyethylene powders, TEFLON, starch, boron nitride, microspheres, such as EXPANCEL (Nobel Industrie), POLYTRAP (Dow Corning) and silicone resin microbeads (TOSPEARLS from Toshiba, for example).
The composition can additionally comprise any additive conventionally used in the cosmetics or dermatological field, such as antioxidants, fragrances, essential oils, preservatives, thickeners, cosmetic active principles, moisturizers, vitamins, dyes, essential fatty acids, sphingolipids, self-tanning agents, such as DHA, or sunscreens.
The composition according to the invention can also comprise at least one active agent, among which may be mentioned agents which are active against microorganisms, in particular with an antiviral, antibacterial or antifungal activity, agents with an antiinflammatory or immunomodulatory activity, agents which antagonize neuromediators or which modulate the release of neuromediators, agents which modulate cell differentiation and/or cell proliferation and/or pigmentation and/or which regulate keratinization, agents which are active in the treatment and/or the prevention of cheilites, antihistamines or cicatrizing agents.
Of course, a person skilled in the art will take care to choose the possible additional compounds and/or their amount so that the advantageous properties of the composition according to the invention are not, or not substantially, detrimentally affected by the envisaged addition.
The composition according to the invention can be provided in the form of a stick, in the form of an oily liquid, optionally gelled or alternatively in the form of a supple paste with a viscosity which can be measured, said dynamic viscosity at 25xc2x0 C. generally being from 1 to 40 Paxc2x7s, measured with a Contraves TV rotary viscometer equipped with an xe2x80x9cMS-r4xe2x80x9d rotor at a frequency of 60 Hz, and better still ranging from 3 to 35 Paxc2x7s.
The compositions according to the invention find an application in particular in the field of making up the skin, semimucous membranes, mucous membranes and/or superficial body growths and are then provided, for example, in the form of a lipstick, of a foundation, of a blusher, of an eyeshadow, of a mascara, of an eyeliner or of a concealer.
They can also be provided in the non-colored form, optionally containing cosmetic or dermatological active principles. They can then in particular be used as a care base for the lips or as a fixing base for a lipstick film, in order to limit the transfer and the migration of a care or makeup film and thus to increase its strength.
The compositions according to the invention can also be provided in the form of a product for caring for the skin, mucous membranes, semimucous membranes and/or superficial body growths, such as a gel, a cream, a balm or a lotion, of a hygiene or pharmaceutical product or alternatively of an antisun or self-tanning product.